CN1104284C

CN1104284C - ERS-10 zeolite and process for its preparation

Info

Publication number: CN1104284C
Application number: CN97103349A
Authority: CN
Inventors: L·卡卢西奥; R·米利尼; G·贝卢西
Original assignee: Eniricerche SpA
Current assignee: Eni Tecnologie SpA
Priority date: 1996-03-21
Filing date: 1997-03-20
Publication date: 2003-04-02
Anticipated expiration: 2017-03-20
Also published as: IT1283284B1; EA000242B1; US5910299A; ITMI960556A0; ITMI960556A1; EP0796821A1; SI0796821T1; EA199700027A1; JPH111319A; GR3031380T3; DK0796821T3; ES2135960T3; DE69700457D1; CN1164439A; ATE183987T1; EP0796821B1; DE69700457T2

Abstract

A novel porous crystalline material, designated ERS-10 zeolite, is described, having in its calcined and anhydrous form a molar composition of oxides corresponding to the formula (I) mM2/nO.zX2O3.YO2 wherein: m is a number between 0.01 and 10, M is H<+> and/or a cation of an alkaline or earth-alkaline metal with valence n, z is a number between 0 and 0.02, X represents one or more elements selected from aluminum, iron, gallium, boron, vanadium, arsenic, antimonium, chromium and manganese and Y represents one or more elements selected from silicon, germanium, titanium, zirconium, characterized by an X-ray diffraction spectrum of the powders shown in table 1. A process is also described for the preparation and purpose of this material.

Description

ERS-10 zeolite and preparation method thereof

The present invention relates to a kind of novel porous crystalline material, ERS-10 zeolite hereinafter referred to as, and relate to a kind of azo spirocyclic compound with general formula (II) expression prepares this zeolite as organic formwork agent method.

The invention still further relates to this material as the application of catalyzer in hydrocarbon conversion process, as the application of molecular sieve and ion-exchanger.

The zeolite in natural origin and synthetic source is the silico-aluminate that the porous crystalline characteristic is arranged, and it is by TO ₄Tetrahedral three-dimensional network is formed, and wherein T can be silicon or aluminium.Existing of trivalent aluminium with tetrahedral coordination in crystal lattice produces excessive negative charge, and it is by basic metal (Na, K, Rb, Li and Cs) ion, alkaline-earth metal (Mg and Ca) ion, organic ammonium positively charged ion or hydrogen ion balance.

It is that known zeolite facies exist that mass crystallization structure major part is arranged.The feature of each zeolite facies is to exist with well-regulated and definite size to be in the special hole that the duct and/or the cage of 3～15 dusts are represented.On the basis of the mean sizes in hole, usually zeolite is divided into " aperture ", " mesopore " and " macropore " zeolite.These features make zeolite be applicable to various fields, as the separation of ion-exchange, gas or liquid mixture, perhaps are used as catalyzer in various hydrocarbon conversion reactions.

Zeolite reacts under hydrothermal condition by the reaction mixture that contains silicon source, aluminium source, organic formwork agent and optional basic metal or alkaline earth salt usually and prepares.Under the condition that is fit to, template plays a part the zeolite synthesis fixed structure that leads, and it is selected from amine and organic quaternary ammonium salt or phosphonium salt usually.

The characteristic of the zeolite that makes depends on the character of composition, reaction conditions and the particularly used organic formwork agent of reaction mixture.

For example, with tetraethyl ammonium hydroxide (Et ₄When NOH) making template, make β zeolite (US.3308069), and with TPAOH (n-Pr ₄When NOH) making template, make ZSM-5 zeolite (U.S.3702886).In some cases, available identical organic formwork agent but synthesize the zeolite (US 4016245, EP-293032, US 4052472) that different structure is arranged with different synthesis conditions.

Have now found that,, use the azo spirocyclic compound of general formula (II) can make novel porous crystalline material as organic formwork agent according to the present invention, ERS-10 zeolite hereinafter referred to as, it is active in catalysis.

In view of the above, the present invention relates to a kind of like this porous crystalline material ERS-10, the anhydrous form of its roasting has the oxide molar of following formula (I) to form:

MM _2/nOzX ₂O ₃YO ₂(I) in the formula, m is the number between 0.01～10, and M is H ⁺And/or valence mumber is alkali metal cation or the alkaline earth metal cation of n, z is the number between 0～0.02, X represents to be selected from one or more elements of aluminium, iron, gallium, boron, vanadium, arsenic, antimony, chromium and manganese, and Y represents to be selected from one or more elements of silicon, germanium, titanium, zirconium.

X is the aluminium that replaced by a kind of element of chosen from Fe, gallium, boron, vanadium, arsenic, antimony, chromium and manganese of aluminium or part preferably, and the silicon that a kind of element of Y to be silicon or part be selected from germanium, titanium, zirconium replaces.

The ERS-10 zeolite of calcined form characterizes with X-ray powder diffraction figure, writes down diffractogram with the vertical side angle meter of charged subpulse counter system, uses CuK ray (λ=1.54178 dusts), and its principal reflection peak is shown in table 1 and Fig. 1.

Table 1d () I/I ₀10011.0±0.1 vs6.80±0.08 w5.79±0.06 w4.59±0.05 m4.29±0.05 vs3.96±0.04 m3.69±0.03 w3.41±0.03 w3.33±0.03 w3.26±0.02 m3.07±0.02 w2.68±0.01 w2.57±0.01 w2.51±0.01 w2.38±0.01 w2.31±0.01 w2.28±0.01 w2.11±0.01 w2.03±0.01 w1.94±0.01 w

Wherein, d presentation surface spacing, I/I ₀The relative intensity of 100 expressions to represent with respect to the percentage ratio of the peak height of the height of highest peak, symbol vs represents very strong intensity (60-100), and s represents strong intensity (40～60), and m represents medium intensity (20～40), and w represents weak intensity (0-20).

The total pore volume of ERS-10 zeolite is 0.13～0.19 a milliliter/gram, and surface-area is about 350 meters ²/ gram.

The Philips EM400T transmission electron microscope (TEM) that use is worked under 120 kiloelectron volts, and use controlled electron beam intensity, with the infringement that prevents that material is possible, it might obtain the image with respect to ERS-10 zeolitic material porous crystalline structure.At first sample is enclosed in the Resins, epoxy, after the sclerosis, the ultramicrotome cutting with diamond blade is housed obtains the thin slice that thickness is 300～700 dusts.Then identical thin slice is deposited on the copper grid, image accumulates on the crystal that is suspended on the grate opening, to avoid overlapping with support.

Fig. 3 represents the Photomicrograph of ERS-10 crystallization aggregate, might obtain the direct visible image of zeolitic material vesicular structure from this figure.Particularly, this structure is determined in the zone that A represents in Fig. 3 Photomicrograph well, and in the figure (Fig. 4) that amplifies relatively, arrange by oblique bi-directional pattern at hole (light color place).Because the resolving power limited (point resolution 3.7 dusts) of used TEM instrument can not record the size in hole exactly.

ERS-10 zeolite of the present invention can make with a kind of like this method, and this method comprises:

(a) preparation optional containing at least aly can be hydrolyzed into X ₂O ₃Compound, at least aly can be hydrolyzed into YO ₂Compound, basic metal or alkaline earth metal cation source or the aqueous solution of its mixture and organic formwork agent (Q), it is characterized in that described template is the azo spirocyclic compound of general formula (II).

In the formula, n and n ' are identical or different, an integer in the expression 3～6, X ^-For being selected from OH ^-, muriate, bromide, fluorochemical and iodide a kind of negatively charged ion, wherein the quantity of each reagent obtains following mol ratio:

YO ₂/X ₂O ₃ 50/1～∞

OH ^-/YO ₂ 0.15/1～0.7/1

Q/YO ₂ 0.1/1～0.5/1

H ₂O/YO ₂ 20/1～60/1

M ⁺/YO ₂ 0.05/1～0.20/1

The solution that obtains in (a) is remained under the sufficient reaction conditions, generate the solid crystal material;

(c) drying solid crystalline material, its anhydrous form have the oxide molar of general formula (III) to form,

YQ ₂OmM _2/nOzX ₂O ₃YO ₂(III) in the formula, y is a numerical value between 0.1～1, and Q is for there being the organic formwork agent of general formula (II), and M is the positively charged ion of basic metal and/or alkaline-earth metal, and m, n, z, X and Y have the as above implication of regulation;

(d) crystalline material of the formula (III) that in step (c), obtains of roasting; And

(e) use H ⁺To small part replacement positively charged ion M, obtain the acid type ERS-10 zeolite of formula (I).

When X be aluminium or part replace aluminium the time, the compound that can be used in the step a) of the inventive method is selected from aluminium isopropylate, Tai-Ace S 150, NaAlO ₂Aluminium isopropylate and Tai-Ace S 150 are preferred.

When Y was the silicon of silicon or part replacement, compound can be selected from tetraethyl orthosilicate (TES), colloidal silica (LUDOX ^), water glass, silicon oxide (AEROSIL ignites ^).TES and LUDOX ^Be preferred.

In the step (a) of the inventive method, sodium hydroxide or potassium hydroxide are preferably used as cationic source.

As organic formwork agent (Q), preferably use the compound of formula (II), wherein n is identical with n ', its value equals 5, X ^-Be OH ^-

In step (a), the adding order of each component of solution is inessential.But, preferably at first make and contain that organic template is optional at least aly to be hydrolyzed into X ₂O ₃Compound and the aqueous solution of cationic source, can be hydrolyzed into YO with at least a then ₂Compound join in this solution.

Under any circumstance, following mol ratio is arranged in the solution that generates:

YO ₂/X ₂O ₃ 50/1～∞

OH ^-/YO ₂ 0.15/1～0.7/1

Q/YO ₂ 0.1/1～0.5/1

H ₂O/YO ₂ 20/1～60/1

M ⁺/YO ₂ 0.05/1～0.20/1

Preferred ratio is:

YO ₂/X ₂O ₃ 80/1～∞

OH ^-/YO ₂ 0.2/1～0.45/1

Q/YO ₂ 0.2/1～0.3/1

H ₂O/YO ₂ 40/1～50/1

M ⁺/YO ₂ 0.09/1～0.15/1

In the step (b) of the inventive method,, preferably about 170 ℃, carry out crystallization at 150～180 ℃.

Reaction times and temperature of reaction, concentration are relevant with other factors, are generally 3～28 days, preferred 7～14 days.Reaction is carried out under autogenous pressure usually, preferably under agitation carries out.

When reaction finishes, as filtering, from mother liquor, isolate the solid crystal phase with conventional technology, with the softening water washing, and in the step (c) of the inventive method, carry out drying.

Drying should be no more than about 170 ℃, carries out such for some time under preferred about 90～120 ℃, during this period of time is enough to fully or almost completely remove moisture.

After drying, there is the crystalline material of general formula (III) that the X-ray diffractogram of measuring is as mentioned above arranged, it has the principal reflection peak among table 2 and Fig. 2.

Table 2d () I/I ₀10011.1±0.1 s6.82±0.08 w5.83±0.06 w4.64±0.05 m4.32±0.05 vs4.00±0.04 s3.72±0.03 m3.42±0.03 w3.35±0.03 w3.27±0.02 m3.08±0.02 w2.70±0.01 w2.58±0.01 w2.54±0.01 w2.39±0.01 w2.32±0.01 w2.29±0.01 w2.12±0.01 w2.11±0.01 w1.94±0.01 w

In the step (d) of the inventive method, the crystalline material of formula (III) is carried out roasting, so that remove the organic formwork agent of occlusion in porous system.This processing is carried out in oxidizing atmosphere usually, for example carries out in air.Maturing temperature in 500～700 ℃ of scopes, preferred 550～650 ℃.Roasting time can change to 20 hours from 4 hours, about 6～15 hours usually.

In the step (e) of the inventive method, usable acid is mineral acid particularly, example hydrochloric acid or with ammonium salt such as ammonium acetate ion-exchange, and then the method for roasting realizes using H ⁺To small part replacement positively charged ion M.

Particularly, can make the zeolite of ammonia type exchange by following three partially disposed: under magnetic stirs, handling 1 hour under 80 ℃ with ammonium acetate solution; Finish the after-filtration product, repeat to wash with softening water; Drying and roasting under these conditions.

X-ray powder diffraction figure through the acid type ERS-10 of roasting zeolite is similar to shown in the table 1.

If desired, methods such as available extrusion are carried out forming processes with catalyzer, make solid be transformed into the required physical form of final application.

In fact, the pattern of visual response device and deciding, ERS-10 zeolitic material of the present invention can use the microsphere particle or the bead of different shapes and pattern.

The ERS-10 catalyzer of acid type of the present invention is active in the chemical reaction that needs the acid catalysis effect, for example in hydrocarbon conversion reactions, as cracking, isomerization, oligomerisation, alkylation, hydrotreatment etc.ERS-10 catalyzer of the present invention also can be used as ion-exchanger and molecular sieve.

The sole purpose of following examples is to illustrate in greater detail the present invention, and never should regard following examples as limitation of the scope of the invention.

Embodiment 1

Under agitation 10.4 gram tetraethyl orthosilicates are added in the solution that contains 45 gram softening waters, 0.204 gram aluminium isopropylate, 0.19 gram sodium hydroxide and 1.71 gram 6-nitrogen spiral shell-[5,5]-undecane oxyhydroxide (Q).These operations are at room temperature carried out.When hydrolysis is complete, obtain the milky white solution of forming by following mol ratio:

SiO ₂/Al ₂O ₃＝100/1

Na ⁺/SiO ₂＝0.095/1

Q/SiO ₂＝0.2/1

H ₂O/SiO ₂＝50/1

OH ^-/SiO ₂＝0.295

In the steel autoclave of then solution being packed into, put into stove and under 170 ℃, autogenous pressure, kept 14 days.Behind the cool to room temperature, from mother liquor, isolate crystallized product with filtering method, with softening water washing, and in stove 120 ℃ dry 2 hours down.

The crystalline material of measuring with the element chemical analysis method composed as follows:

67SiO ₂∶1Al ₂O ₃∶0.5Q ₂O∶0.3Na ₂O∶7H ₂O

Carry out the X-ray powder diffraction analysis with the vertical goniometer (Phillips) that electronic impulse counting system is housed, use CuK ray (λ=1.54178 dusts).The spectrogram of this sample is shown in table 3.

Table 3

d() 100.I/I ₀ 11.9±0.10 41 6.82±0.08 3 5.83±0.06 2 4.64±0.05 39 4.32±0.05 100 4.00±0.04 46 3.72±0.03 21 3.42±0.03 12 3.35±0.03 17 3.27±0.02 40 3.08±0.02 4 2.70±0.01 5 2.58±0.01 2 2.54±0.01 4 2.39±0.01 22.32±0.01 32.29±0.01 32.12±0.01 22.11±0.01 32.03±0.01 12.00±0.01 21.94±0.01 41.91±0.01 31.87±0.01 21.85±0.01 1

Then in airflow, with crystallized sample 550 ℃ of roastings 5 hours.Chemical analysis obtains following composition:

67SiO ₂∶1Al ₂O ₃∶0.3Na ₂O

Use ammonium acetate solution 80 ℃ of following re-treatments the product of roasting then, with the softening water washing and 550 ℃ of following roastings 5 hours, so that be exchanged into acid type.

The X-ray powder diffraction spectrogram of this acid type sample is shown in table 4.

Table 4d () I/I ₀10010.97±0.10 1006.79±0.08 125.79±0.06 84.59±0.05 474.29±0.05 793.96±0.04 393.69±0.03 173.41±0.03 93.33±0.03 163.26±0.02 373.07±0.02 42.68±0.01 42.57±0.01 12.50±0.01 72.38±0.01 32.31±0.01 22.28±0.01 22.11±0.01 32.03±0.01 11.99±0.01 11.94±0.01 21.90±0.01 2

Measure the existence that confirms lewis' acid and bronsted acid with pyridine as the acidity that the test molecule carries out.

Embodiment 2

Adopt the step identical, use 0.408 to restrain aluminium isopropylate with embodiment 1.When hydrolysis finishes, obtain the milky white solution of forming by following mol ratio:

SiO ₂/Al ₂O ₃＝50/1

Na ⁺/SiO ₂＝0.0475/1

Q/SiO ₂＝0.2/1

H ₂O/SiO ₂＝45/1

OH ^-/SiO ₂＝0.2475/1

X-ray diffractogram after drying and the roasting is the spectrogram shown in the similar table 3 and 4 respectively.

Embodiment 3

With 0.315 gram Al ₂(SO ₄) ₃16H ₂O and 10 gram Ludox ^AS (30%) is added in the solution that contains 33.5 gram softening waters, 0.19 gram sodium hydroxide and 1.71 gram 6-nitrogen spiral shell-[5,5]-undecane oxyhydroxide.

After hydrolysis fully, make the shallow milky white solution of forming by following mol ratio:

SiO ₂/Al ₂O ₃＝100/1

Na ⁺/SiO ₂＝0.095/1

Q/SiO ₂＝0.2/1

H ₂O/SiO ₂＝45/1

OH/SiO ₂＝0.295/1

The steel autoclave of then solution being packed into is put into stove and was kept 14 days under 170 ℃, autogenous pressure.Behind the cool to room temperature, from mother liquor, isolate crystallized product with filtration method, with softening water washing, in 120 ℃ of stoves dry 2 hours then.

The X-ray powder diffraction data of this sample are listed table 3 in.

Roasting is after 5 hours in 550 ℃, air, be exchanged into acid type with ammonium acetate solution 80 ℃ of following re-treatments, 120 ℃ down dry, roasting 5 hours in 550 ℃ of following air then, obtain pure ERS-10 zeolite facies, characterize fully and that table 4 is listed is similar with X-ray powder diffraction.

Embodiment 4

Adopt the step identical, use 0.173 gram aluminium isopropylate and 10.4 to restrain tetraethyl orthosilicates with embodiment 1.

Hydrolysis obtains the shallow milky white solution of being made up of following mol ratio after finishing:

SiO ₂/Al ₂O ₃＝120/1

Na ⁺/SiO ₂＝0.095/1

Q/SiO ₂＝0.2/1

H ₂O/SiO ₂＝45/1

OH/SiO ₂＝0.295/1

After the dry and roasting, this material has respectively and table 3 and 4 listed identical X-ray powder diffraction data.

Embodiment 5

Adopt the step identical, use 0.128 gram aluminium isopropylate and 10.4 to restrain tetraethyl orthosilicates with embodiment 1.

SiO ₂/Al ₂O ₃＝160/1

Na ⁺/SiO ₂＝0.095/1

Q/SiO ₂＝0.2/1

H ₂O/SiO ₂＝45/1

OH/SiO ₂＝0.295/1

After the dry and roasting, the X-ray powder diffraction data respectively with table 3 and 4 listed identical.

Embodiment 6

10.4 gram tetraethyl orthosilicates are added in the solution that contains 45 gram softening waters, 0.19 gram sodium hydroxide and 1.71 gram 6-nitrogen spiral shell-[5,5]-undecane oxyhydroxide.

After hydrolysis fully, make the clear solution of forming by following mol ratio.

SiO ₂/Al ₂O ₃＝x

Na ⁺/SiO ₂＝0.095/1

Q/SiO ₂＝0.2/1

H ₂O/SiO ₂＝50/1

OH/SiO ₂＝0.295/1

The steel autoclave of then solution being packed into is put into stove, keeps 7 days under 170 ℃, autogenous pressure.Behind the cool to room temperature, from mother liquor, isolate crystallized product with filtration method, with the softening water washing, following dry 2 hours at 120 ℃ then.The main X-ray powder diffraction data of this sample are listed table 3 in.

Roasting obtained pure ERS-10 zeolite facies after 5 hours in 550 ℃ of following air, characterized the listed result of all fours table 4 with X-ray powder diffraction.

Embodiment 7 (contrast)

15.6 gram tetraethyl orthosilicates are added to contain 27 gram softening waters, 0.306 gram aluminium isopropylate and 3.85 gram 6-nitrogen spiral shell-[5,5]-undecane oxyhydroxide.When hydrolysis is complete, obtain the complete clear solution of forming by following mol ratio:

SiO ₂/Al ₂O ₃＝100/1

Q/SiO ₂＝0.3/1

H ₂O/SiO ₂＝20/1

With the solution steel autoclave of packing into, put into stove, under 170 ℃, autogenous pressure, kept 14 days.Behind the cool to room temperature, from mother liquor, isolate crystallized product with filtration method, with the softening water washing, following dry 2 hours at 120 ℃ then.X-ray powder diffraction figure shows has ZSM-12 zeolite facies (MTW) to exist.

This result shows that the existence of sodium is necessary for making the ERS-10 zeolite.

Embodiment 8 (contrast)

10.4 gram tetraethyl orthosilicates are added in the solution that contains 40.5 gram softening waters, 0.68 gram aluminium isopropylate, 0.62 gram sodium hydroxide and 1.71 gram 6-nitrogen spiral shell-[5,5]-undecane oxyhydroxide.

When hydrolysis is complete, obtain the white suspension of the homogeneous formed by following mol ratio:

SiO ₂/Al ₂O ₃＝30/1

Na ⁺/SiO ₂＝0.31/1

Q/SiO ₂＝0.2/1

H ₂O/SiO ₂＝45/1

OH/SiO ₂＝0.51/1

Solution is packed in the steel autoclave, put into stove, and under 170 ℃, autogenous pressure, placed 14 days.Behind the cool to room temperature, from mother liquor, isolate crystallized product with filtration method, with the softening water washing, following dry 2 hours at 120 ℃ then.X-ray powder diffraction figure shows mordenite is arranged (MOR) exists.

Embodiment 9

The material through roasting that obtains among the embodiment 1 can be used as molecular sieve.Use NH ₃, normal hexane, hexanaphthene and sym-trimethylbenzene adsorb measurement as the test molecule.These measurements are carried out according to the following steps:

-with powder at 500 ℃, 6 * 10 ^-5The millibar decompression activates 1 hour down;

-under 23 ℃, identical vacuum tightness, system was stablized 16 hours;

-add test molecular vapors in a small amount down at 23 ℃, until balance;

-with testing the known coefficient of expansion of molecule and balance piezometry adsorptive capacity.

Be shown in table 5 with the loading capacity that the gram adsorbed product/100 gram catalyzer are represented.

Table 5

The test molecule	Size (dust)	Adsorptive capacity (gram/100 gram ERS-10)
The test molecule	Size (dust)	Adsorptive capacity (gram/100 gram ERS-10)	NH ₃	2.6	2.35
n-C ₆H ₁₄	4.3	3.10	NH ₃	2.6	2.35
n-C ₆H ₁₄	4.3	3.10	C ₆H ₁₂	6.0	2.15
Sym-trimethylbenzene	8.1	0.45	C ₆H ₁₂	6.0	2.15

^*Equilibrium pressure is 0.6 millibar

Claims

1. porous crystalline material that is called the ERS-10 zeolite, this material has the oxide molar of general formula (I) to form through the anhydrous form of roasting:

MM _2/nOzX ₂O ₃YO ₂(I) in the formula, m is the number in 0.01～10, and M is H ⁺And/or valence mumber is alkali metal cation or the alkaline earth metal cation of n, z is the number in 0～0.02, X represents to be selected from one or more elements of aluminium, iron, gallium, boron, vanadium, arsenic, antimony, chromium and manganese, Y represents to be selected from one or more elements of silicon, germanium, titanium, zirconium, and this material characterizes with the X-ray powder diffraction figure shown in the following table 1:

2. according to the porous crystalline material of claim 1, wherein M is selected from sodium, potassium, hydrogen or its mixture.

3. according to the porous crystalline material of claim 1, wherein X is aluminium or the aluminium that partly replaced by the element of chosen from Fe, gallium, boron vanadium, arsenic, antimony, chromium and manganese.

4. according to the porous crystalline material of claim 1, wherein Y is the silicon that silicon or the element that is selected from germanium, titanium and zirconium partly replace.

5. method for preparing the porous crystalline material ERS-10 of claim 1, this method comprises:

(a) preparation optional containing at least aly can be hydrolyzed into X ₂O ₃Compound, at least aly can be hydrolyzed into YO ₂The cationic source of compound, basic metal or alkaline-earth metal and the aqueous solution of a kind of organic formwork agent (Q), it is characterized in that described template is the azo spirocyclic compound that general formula (II) is arranged In the formula, n and n ' are identical or different, an integer in the expression 3～6, X ^-For being selected from OH ^-, muriate, bromide, fluorochemical and iodide negatively charged ion, and wherein the amount of each reagent has following mol ratio:

YO ₂/X ₂O ₃ 50/1～∞

OH ^-/YO ₂ 0.15/1～0.7/1

Q/YO ₂ 0.1/1～0.5/1

H ₂O/YO ₂ 20/1～60/1

M ⁺/YO ₂ 0.05/1～0.20/1

The solution that obtains in (a) was reacted 3-28 days down at 150-180 ℃, generate the solid crystal material;

(c) be no more than 170 ℃ of following drying solid crystalline materials, the crystalline material of this anhydrous form has the oxide molar of general formula (III) to form

YQ ₂OmM _2/nOzX ₂O ₃YO ₂(III) in the formula, y has 0.1～1 numerical value, and Q is the organic formwork agent of general formula (II), and M is basic metal and/or alkaline earth metal cation, and m, n, z, X and Y have the identical definition of stipulating above;

(d) crystalline material (III) that obtains in step (c) at 500-700 ℃ roasting temperature is 4-20 hour, and last

(e) use H ⁺To small part replacement positively charged ion M, obtain the acid type ERS-10 zeolite of general formula (I).

6. according to the method for claim 5, it is characterized in that, in step (a), can be hydrolyzed into X ₂O ₃Compound be selected from aluminium isopropylate, Tai-Ace S 150, NaAlO ₂

7. according to the method for claim 6, wherein aluminum compound is selected from aluminium isopropylate and Tai-Ace S 150.

8. according to the method for claim 5, it is characterized in that, in step (a), can be hydrolyzed into YO ₂Compound be the silicon compound that is selected from tetraethyl orthosilicate, colloidal silica, water glass, the silicon oxide of igniting.

9. method according to Claim 8 is characterized in that, silicon compound is selected from tetraethyl orthosilicate, colloidal silica.

10. according to the method for claim 5, it is characterized in that cationic source is sodium hydroxide or potassium hydroxide.

11. the method according to claim 5 is characterized in that, organic formwork agent (Q) is for there being the compound of formula (II), and wherein n is identical with n ', all is 5, X ^-Be OH ^-

12. the method according to claim 5 is characterized in that, the quantity of each component of solution has following mol ratio:

SiO ₂/X ₂O ₃ 80/1～∞

OH ^-/SiO ₂ 0.2/1～0.45/1

Q/SiO ₂ 0.2/1～0.3/1

H ₂O/SiO ₂ 40/1～50/1

M ⁺/SiO ₂ 0.09/1～0.15/1

13. the method according to claim 5 is characterized in that, temperature of reaction is about 170 ℃, and the reaction times is 7～14 days.

14. the method according to claim 5 is characterized in that, described drying is carried out under 90～120 ℃.

15. the method according to claim 5 is characterized in that, roasting was carried out under 550～650 ℃ 6～15 hours.

16. the method according to claim 5 is characterized in that, in step (e), replaces with mineral acid or ammonium salt ion-exchange.

17. according to the method for claim 16, wherein said mineral acid is a hydrochloric acid.

18. according to the method for claim 16, wherein said ammonium salt is an ammonium acetate.

19. zeolite precursor that its anhydrous form has general formula (III) oxide molar to form

YQ ₂OmM _2/nOzX ₂O ₃YO ₂(III) in the formula, y has 0.1～1 numerical value, and Q is for there being the organic formwork agent of general formula (II) In the formula, n and n ' are identical or different, are an integer in 3～6, X ^-For being selected from OH ^-, muriate, bromide, fluorochemical and iodide negatively charged ion, M is that valence mumber is basic metal or the alkaline earth metal cation of n, z is the number in 0～0.02, X represents to be selected from one or more elements in aluminium, iron, gallium, boron, vanadium, arsenic, antimony, chromium and the manganese, Y represents to be selected from one or more elements in silicon, germanium, titanium, the zirconium, and this zeolite precursor is represented with the X-ray powder diffraction figure shown in the following table 2:

20. claim 1～4 each porous crystalline material ERS-10 or each the porous crystalline material ERS-10 of method preparation of claim 5-18 as molecular sieve, ion-exchanger and the purposes in hydrocarbon conversion catalytic process.